Solid, pulverulent to granular compositions containing bleaching activators

ABSTRACT

SOLID, PULVERULENT TO GRANULAR COMPOSITIONS USEFUL FOR THE PREPARATION OF AQUEOUS COLD-BLEACHING BATHS, ESPECIALLY COLD-BLEACHING WASHING LIQUORS FOR TEXTILES COMPRISING (A) FROM 5% TO 100% BY WEIGHT OF AN ACTIVATOR COMPONENT CONSISTING OF AN ACTIVATOR FOR PRE-COMPOUNDS IN THE FORM OF PARTICLES SURROUNDED WITH A COATING SUBSTANCE INERT TO THE ACTIVATOR, SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE COMPOUNDS AND WATER-INSOLUBLE COMPOUNDS, SAID ACTIVATOR CONSTITUTING FROM 5% TO 50%, PREFERABLE 15% TO 40% BY WEIGHT, AND SAID COATING SUBSTANCE CONSTITUTING FROM 50% TO 95%, PREFERABLY 60% TO 85% BY WEIGHT, OF THE ACTIVATOR COMPONENT, AND (B) FROM 0 TO 95% BY WEIGHT OF OTHER CUSTOMARY CONSTITUENTS OF BLEACHING AGENTS OR WASHING COMPOSITIONS WITH BLEACHING ACTION; AS WELL AS THE METHOD OF PRODUCING THE COATED ACTIVATOR COMPONENT.

Mn. 29, 1974 WEBER ETAL 501110, PULVERULENT TO GRANULAR 'COMIOSL'JII'ONSCONTAINING BLBACHING 'ACTIVATORS Flled Sept 22, 1971 INVENTORS V RUDOLFWEBER BY ANGELIKA OPGENQORTH ATTORNEYS United States Patent 7 3,789,002SOLID, PULVERULENT TO GRANULAR COMPOSI- TIONS CONTAINING BLEACHINGACTIVATORS Rudolf Weber, Dusseldorf-Holthausen, and Angelika Opgenoorth,Dusseldorf, Germany,'assignors to Henkel 8: Cie GmbH, Dusseldorf,Germany Filed Sept. 22, 1971, Ser. No. 182,748 Claims priority,application Germany, Oct. 1, 1970, P 20 48 331.2 Int. Cl. Clld 7/56 US.Cl. 252-99 12 Claims ABSTRACT OF THE DISCLOSURE Solid, pulverulent togranular compositions useful for the preparation of aqueouscold-bleaching baths, especially cold-bleaching washing liquors fortextiles comprising (A) from to 100% by weight of an activator componentconsisting of an activator for per-compounds in the form of particlessurrounded with a coating substance inert to the activator, selectedfrom the group consisting of water-soluble compounds and water-insolublecompounds, said activator constituting from 5% to 50%, preferably 15% to40% by weight, and said coating substance constituting from 50% to 95%,preferably 60% to 85% by weight, of the activator component, and (B)from 0 to 95% by weight of other customary constituents of bleachingagents or washing compositions with bleaching action; as well as themethod of producing the coated activator component.

THE PRIOR ART Inorganic percompounds, especially perborates, are knownas the active component of numerous bleaching agents, for example thoseused for the bleaching and possibly for the simultaneous washing oftextiles. Such bleaching agents have the disadvantage, however, thattheir bleaching action at temperatures below 80 C. is relatively low.The addition of organic activators to such bleaching agents containingpercompounds is known. These activators act in such a manner that theactive oxygen of the percompound also becomes effective at tem peraturesbelow 80 C.

The organic activators used are generally compounds which contain N-acylor O-acyl residues in the molecule, and which exert their activatingaction on the organic percompounds on contact with these in the washingliquor. The exact mode of action of the activators is not known, but itis assumed that organic per-acids are formed by reaction of the organicactivators with the inorganic percompounds, which acids then liberateactive oxygen by decomposition. Since this action occurs in the presenceof water, compositions containing inorganic percompounds and activatorcombined must be kept under substantially anhydrous conditions.

OBJECTS OF THE INVENTION An object of the invention is the preparationof solid, pulverulent to granular compositions useful in the preparationof cold-bleaching liquors, especially of coldbleaching washing liquorswhich are stable on storage under humid conditions.

Another object of the invention is the preparation of solid, pulverulentto granular activator component compositions useful in the preparationof aqueous cold-bleaching baths consisting essentially of an activatorfor active oxygen derived from compounds yielding H 0 in aqueoussolution, said activator being in the form of particles substantiallysurrounded with an at least water-dispersible coating substance inert tosaid activator selected from the group consisting of water-solublecompounds and 3,789,002 Patented Jan. 29,, 1974 water-insolublecompounds, said activator constituting from 5% to 50% by weight and saidcoating substance constituting from 50% to by weight, of the activatorcomponent.

A further object of the present invention is the development of aprocess for the production of solid, pulverulent to granular activatorcomponent composition useful in the preparation of aqueouscold-bleaching baths consisting of, in any sequence, wetting a solid,pulverulent to granular activator, for active oxygen derived fromcompounds yielding H 0 in aqueous solution with an aqueous liquid andadmixing an at least water-dispersible, solid coating substance inert tosaid activator therewith, the relative proportions of said activator,said aqueous liquid and said solid coating substance being selected sothat the water present is bound by forces selected from the groupconsisting of surface forces and water of crystallization, and saidactivator constitutes from 5% to 50% by weight and said coatingsubstance including bound water constitutes from 50% to 95% by weight,of the activator component.

A yet further object of the present invention is the preparation ofsolid, pulverulent to granular compositions useful in the preparation ofaqueous cold-bleaching baths, especially cold-bleaching washing liquorsfor textiles consisting essentially of (I) from 5% to 95% by weight ofan activator component consisting of an activator for active oxygenderived from compounds yielding H 0 in aqueous solution, being in theform of particles substantially surrounded with with an at leastWater-dispersible coating substance inert to said activator selectedfrom the group consisting of water-soluble compounds and Water insolublecompounds, said activator constituting from 5% to 50% by weight and saidcoating substance constituting from 50% to 95 by weight, of theactivator component, and (II) from 5% to 95 by Weight of at least onecompound selected from the group consisting of (a) alkali metal buildersalts, (b) percompounds giving H 0 in aqueous solutions and stabilizersfor percompounds, (c) tensides selected from the group consisting ofanionic surface-active compounds, nonionic surface-active compounds andamphoteric surface-active compounds, ((1 optical brighteners, (e)water-soluble organic builder salts, (f) antimicrobial agents, (g) soilsuspension agents, (h) enzymes, (i) foam stabilizers, (j)non-surface-active foam inhibitors, (k) textile softeners, (l) corrosioninhibitors, and (to) water.

These and other objects of the invention will become more apparent asthe description thereof proceeds.

THE DRAWING FIG. 1 is a flow diagram of one embodiment of the process ofcoating the activator.

DESCRIPTION OF THE INVENTION The invention relates to agents for thepreparation of cold-bleaching liquors, particularly cold-bleachingactive washing liquors.

In one aspect, therefore, the present invention provides a solidpulverulent or granular composition useful for the preparation ofcold-bleaching baths, especially coldbleaching washing liquor,comprising:

% to 5% by weight of an activator component comprising an activator forpercompounds in the form of particles which are surrounded with acoating of a water-soluble and/or water-insoluble substance inert to theactivator, while the activator constitutes 5% to 50%, preferably 15% to40%, by weight and the coating material constitutes 95 to 50%,preferably 85% to 60%, by Weight of the activator component, and to 95%by weight of other customary constituents of bleaching agents orbleaching washing compositions.

The coated activators according to the invention are specially suitablefor the preparation of bleaching and washing compositions containingpercompounds, which thereby attain a considerably improved stabilityduring storage.

The activators for percompounds utilizable according to the inventionare certain compounds of the N-acyl and O-acyl type as well as carbonicacid esters of pyrocarbonic acid esters, indicated below under (a) to(1), which have an activation value for compounds in the Per-AcidFormation Test of at least 3, preferably at least 4.5.

Per-acid formation test The activation value (=titre) for the activatorsis determined in the following way:

Solutions which contain 0.615 gm./ liter of NaB O H O 3H O (4 mol/liter)and 2.5 gm./liter of Na P O -10H O, are heated to 60 C., and then aremixed with 4 mmol/liter of activator and maintained at the saidtemperature for 5 minutes with stirring. Then 100 ml. of this liquid isadded to a mixture of 250 gm. of ice and ml. of glacial acetic acid andtitrated immediately after addition of 0.35 gm. of potassium iodide with0.1 N sodium thiosulfate solution, using starch as indicator. Under thegiven experimental conditions, for a 100% activation of the peroxideused, 8.0 ml. of thiosulfate solution are con-' sumed, the titre is 8.0.This maximum value is of course seldom attained. Good activators have atitre of at least 4.5, preferably from 5 to 7. Useful results are oftenobtained with activators having a titre of at least 3.0.-

Activators of the N-acyl or O-acyl compounds type contain an acylresidue RCO-, in which R represents optionally substituted hydrocarbonresidues with 1 to 8 carbon atoms. If the residues R are aliphatic, theypreferably have 1 to 3 carbon atoms, and if they are aromatic,

they may contain up to 8 carbon atoms. Consequently,

the residue R is preferably one of the following: lower alkyl, such asmethyl, ethyl, n-propyl or isopropyl; phenyl; alkylphenyl such as toluylor xylyl residues. Suitable substituents are C alkoxy groups, halogenatoms, nitro or nitrile groups; when R is an aroamtic residue it may bechloroand/or nitro-substituted, especially m-chloro or morp-nitro-substituted. Such substituents are, for example, chloroalkylhaving 1 to 3 carbon atoms, m-chlorophenyl, p-nitrophenyl, andp-methoxyphenyl.

Of the activators described below, compounds with a melting point of atleast 70 0., preferably at least 100 C. and especially at least 150 C.,are specially suitable. Further the equivalent weight of these compoundsshould be not more than 170, preferably not more than 130 and especiallynot more than 110 (the equivalent weight is here the quotient of themolecular weight and the number of RCO- residues present in the moleculewhere the compound is N-acylated or O-acylated).

The types of compound mentioned under (a) to (j) are useful activatorsaccording to the invention. In the formulae the numbered residues R havethe meaning given for R above unless specifically otherwise indicated.If several residues R are present in a molecule, they may be the same ordifferent.

(a) N-diacylated amines of the Formula I, in which I X represents aresidue R or one of the residues Ia, lb,

From this class of compounds, N,N,N',N-tetraacetyl-' methylenediamiue(melting point 9295 C.), N,N,N', N'-tetraacetylethylenediamine,N,N-diacetylaniline and N,N-diacetyl-p-toluidine are named as examples.

(b) N-alkyl-N-sulfonyl-carbonamides of Formula II, which R preferablysignifies a C alkyl residue.

Suitable compounds are, for example, 1,3-diacetyl-5,5-dimethylhydantoin, 1,3 dipropionylhydantoin (M.P.

104.5 to 106? C.) and 3-benzoylhydantoin-l-acetic acid ethyl ester.

v ((1) Cyclic N-acylhydrazides'of Formula 'IV,.in which the two'nitrogenatoms are part of a 5- or 6-membered hetero-ring from the group ofmaleic acid hydrazide, phthalic acid hydrazide, triazole or urazole.

C}|IC 0 Ru (1 V A suitable compound is, for example, mono-acetyl-maleicacid hydrazide.

(e) Carbonic acid esters of Formula V, in which X representsv'anelectron-attracting residue, preferably selected from the groupp-carboxyphenyl, p-sulfophenyl or alkoxycarbonyl with 1 to 4 carbonatoms in the alkoxy group: I

X -OCOOR For example, p-ethoxycarbonyloxy-benzoic acid (M.P.

.157" C.) is utilizable.

(f) Pyrocarbonic acid esters of C to C alkanols as, for example,pyrocarbonic acid ethyl ester. (g) Triacyl-cyanurates of Formula VI Forexample, triacetylor tribenzoyl-cyanurate.

(h) Optionally substituted anhydrides of benzoic or phthalic acids,especially beuzoic anhydride itself or mchloro-benzoic anhydride (M.P.95 C.).

(i) 0,N,N-trisubstituted hydroxylamines of Formula VII, in which Rrepresents a residue R, preferably a methyl or ethyl residue, anoptionally substituted aryl residue or the group VIIa, while X and Xrepresent one of the residues R-CO--, R-SO or one of the above-describedaromatic residue, or each can be linked with the corresponding residue Ror R to give a succinyl or phthalyl residue and n signifies a wholenumber from to 2.

Activators of this type are, for example, O-benzoyl-N,Nsuccinyl-hydroxylamine (M.P. 137-l39 C.), O-acetyl-N,N-succinyl-hydroxylamine (M.P. 132-134 C.), O-pmethoxybenzoyl N,Nsuccinyl-hydroxylamine (M.P. l42145 C.),O-p-nitrobenzoyl-N,N-succinyl-hydroxylamine (M.P. 212215 C.) andO,N,N-triacetyl-hydroxylamine.

(l) N,N' diacyl sulfurylamides of Formula VIII, in which R and Rpreferably represent C alkyl residues or aryl residues such as phenyl,while R and R preferably represent C alkyl residues, especially C alkylresidues.

R es

N,N'-dimethyl-N,N'-diacetyl-sulfurylamide (M.P. 58 to 60 C.) andN,N'-diethyl-N,N'-dipropionyl-sulfurylamine (M.P. 95-97 C.) may bementioned as examples.

(k) 1,3-diacy1-4,5-diacyloxy-imidazolidines of Formula IX, in which Xrepresents hydrogen or R, and R and R represent hydrogen or R.

O C-Rs4 (VIII) O Ros (IX) To these belong:1,3-diformyl-4,5-diacetoxy-imidazolidine (M.P. 160 -165.5 C.),l,3-diacetyl-4,5-diacetoxy-imidazolidine (M.P. 139-1405 C.),1,3-diacetyl-4,5dipropionyloxy-imidazolidine (M.P. 85-87 C.).

(l) Acylated glycolurils of the general Formula X, in which X representsthe residue R or RCO.

It is often sufficient to activate only a part of the activeoxygenpresent. For this, additions of activator of at least 0.1, preferably ofa least 0.2 mol of activator per gram-atom of active oxygen aresufficient. If the greatest possible activation of the active oxygen isrequired, the addition of activator can be increased up to 4 mols,preferably up to 3 mols. However, it is preferred to work with 0.3 to 2mols of activator per gram-atom of active oxygen. These amounts can, ofcourse, be varied according to the activity of the particular activatorused.

The activator component according to the invention is present in apulverulent to granular state, i.e. in a particle size range of 0.1 to 3mm., preferably to at least 70% in a particle size range of 0.3 to 2 mm.The expression pulverulent to granular is here in its general meaning,as it is ordinarily used in connection with washing, bleaching andcleaning compositions, so that particle sizes of fine powdered tocoarsely granular inclusive of granulates or agglomerates are included.

Suitable coating materials for coating the activators are water-solublepartly hydratable salts and/ or water-insoluble inorganic or organicpulverulent materials with a large surface area. The coatings may alsocontain the below described water-soluble or water-dispersiblecellulose, protein and starch derivatives, alkali metal silicates,surface-active compounds and dispersing agents.

The invention also relates to a. process for the preparation of thesolid pulverulent to granular activator component substances which aresuitable for the production of cold-acting bleaching baths. This processis characterized in that the activator is wetted with aqueous liquidsand then mixed with solid coating substances in any sequence, therelative proportions of activator, aqueous liquid and solid coatingsubstance being chosen so that the water present is bound by surfaceforces and/or as water of crystallization, and the granulate oragglomerate thus obtained is admixed with the further constituentsoptionally contained in the compositions according to the invention,possibly after an additional drying.

The most important solid coating substance for the process of theinvention are calcined water-soluble inorganic salts which are able tocrystallize with the binding of Water of crystallization, for example,the carbonates, ortho-, pyroand poly-phosphates, and the sulfates of thealkali metals, especially of sodium and potassium. Mixtures of differentsalts can also be used, and the mixtures may contain the same ordifferent cations and/or the same or different anions. Watersolublesalts are preferably used which form the usual constituents of bleachingagents, especially bleaching washing compositions and washingassistants, and which are further described in detail below as buildersalts for washing compositions. The water-insoluble coating substancesof inorganic or organic pulverulent materials with an large activesurface are, for example, inorganic materials such as microcrystallinesilicic acid, magnesium oxide, magnesium silicate, tin oxide, tinsilicates, or titanium dioxide, and also organic plastic powders suchas, polyethylene and polypropylene powders. Here also coating substancesare preferred which are the usual washing composition constituents, forexample the said oxides and silicates serving as water-insolublestabilizers for percompounds which are also described in more detaillater.

Suitable aqueous liquids, with which the activator is wetted are purewater; aqueous solutions preferably saturated, of the above-mentionedwater-soluble salts, prefably binding Water of crystallization; aqueoussolutions or dispersions of colloidal adhesives such as cellulosederivatives as for example, carboxymethylcellulose, methylorhydroxy-ethyl-cellulose, protein and starch derivatives such as, forexample, gelatine, casin, egg albumen,

groundnut or soya bean proteins, dcxtrins, tragacanth,

pectin, agar-agar, alginates, etc; and aqueous solutions of thewater-soluble alkali metal silicates. Also useful are 7 the queousdispersions or solutions of the usual surfaceactive compounds anddispersing agents known as constituents of washing compositions anddescribed in more detail below, especially the non-ionic surface-activecompounds and dispersing agents such as, for example, fatty alcoholpolyglycol ethers, alkylaryl-polyglycol ethers, ethylene oxide-propyleneoxide polymers, polyethylene gycols and polyvinyl alcohols.

When the above-mentioned water-soluble salts binding water ofcrystallization are used as coating substances according to the processof the invention, the amount of water to be used is such that theinorganic salts in the finished agglomerate have a degree of hydrationof from to 90%, preferably from to 50%, of the highest possiblehydration for the solid stable hydrate.

The partical size range of the particles of the activator and the solidcoating substance to be processed lies in general in the range of 0.005to 1 mm., preferably from 0.01 to 0.8 mm. but the process according tothe invention is not restricted to the use of particles of the particlesize range indicated.

The composition according to the invention prepared by use ofwater-soluble salts binding water of crystallization contains from 5% to100% by weight of an activator component of the following composition:

5% to 50%, preferablyto 40% by weight of activator 95 to 30%, preferably85% to 35% by weight of watersoluble salts containing water ofcrystallization with a degree of hydration of 5% to 90%, preferably 10%to 50%.

0% to 15%, preferably 1% to 10% by weight of the above-mentionedsubstances suitable for forming solutions or dispersions with water forwetting the activator.

The composition prepared by use of water-insoluble solid coatingsubstances contains from 5% to 100% by weight of an activator componentof the following composition:

5% to 50%, preferably 15% to 40% by weight of activator,

95% to preferably 82% to by weight of water-insoluble solid pulverulentcoating substances, of large surface area,

0% to preferably 2% to 10% by weight of water,

0% to 20%, preferably 1% to 10% by weight of the above-mentionedsubstances forming together with water suitable solutions or dispersionsfor wetting the activator.

According to a preferred form of the process of the invention, acylatedglycolurils, especially tetraacetyl-glycoluril, are used as theactivator. Water and calcined sodium tripolyphosphate or aqueousgelatine solution and calcined sodium tripolyphosphate or aqueouscarboxymethyl-cellulose solution and pulverulent magnesium oxide havebeen found particularly good for the granulation coating of theseglycolurils.

For carrying out the process of the invention an apnozzles are shaped asfar as possible so that the sprayed liquid is distributed as evenly aspossible over the surface occupied by the moving mass of particles.Moreover,

nozzles which send out a fan-shaped jet of liquid have provedsatisfactory. In such case the fan of sprayed liquid should suitablyform a right angle with the direction of movement of the material.

. The apparatus may be provided with stationary or rotating fittings,which however should proceed largely in the direction of the movement ofthe material to be granulated, so that as little friction as possiblewith the material passing through occurs, the continuous run through ofthe material is favored and contact of already formed granules withfresh or only partly granulated material is largely prevented. Suchfittings are, for example, screw conveyors, stripping or guiding platesextending in the direction of movement of the material on which thematerial slides past. These fittings ensure that the time each particleremains in the apparatus is as near as possible to the average time ofthe whole material therein. The time of the material may vary withinwide limits from, for example, 5 to 200 seconds.

If it is desired to cool the granules, this may be effected in any knownapparatus, as for example cooling towers and cooling drums. Cooling ofthe material whirled up or conveyed with or against a stream of air hasproved specially suitable. The material to be cooled can also be allowedto trickle down a vertical tube or tower and cold air blown against itwith a speed which is a little less than the speed of fall of thegranules. In this way the cooling of the granules can be combined withan air separation of the fines.

An apparatus for carrying out the process according to the invention isshown in FIG. 1. The activator to be granulated is in the stock vessel 1and runs via the dosing device 2 into the funnel 3, which conveys it tothe granulating device 4, which is an obliquely positioned rotatingdisc. The solid coating substance to be used in the granulation is inthe stock vessel 5 and is conveyed via the dosing device 6 into thefunnel 3, where it is mixed with the activator. The aqueous liquid usedfor wetting is in the pressure vessel 7 and, as described, compriseseither of water, a solution of the salt crystallizing with binding ofwater of crystallization present in the stock vessel5 or of another, orof a solution or dispersion of a surface.- active compound or dispersingagent. The vessel 7 is via the line 8 and the reducing valve 9 put underpressure by a gas so that the liquid arrives at the nozzle 12 via theline 10 which may be provided with a heating arrangement 11, and issprayed on the granulation disc 4. The granulated material runs over theedge of the disc into the funnel 13, and from there into the pipe 14 andthe vessel 15. Air is forced into this vessel 15 from the fan 16 via theline 17 and the throttle valve 18. Part of this air flows into the pipe14 into the just formed granulate in countercurrent at such a speed thatthe speed of fall of the granulate in the pipe 14 is greatly reduced,the granulate being cooled at the same time. The granulate falls to thebottom of the container 15 and in the lower funnel-shaped part of thevessel 15 is conveyed by the remainder of the air forced into thisvessel into the descending line 19, which is connected with the lowerpart of the rising line 20. Air from the fan 27 is sucked through thelower open end of the rising line 20 at such speed that the whole of thegranulate is lifted through this rising line into the separator 21. Theair leaves the separator through the line 22 and goes to the cyclone 23,where the fine, ungranulated or not sufficiently granulated particlesand particles entrained by the stream ofair are separated and arereturned through the line 24 to the funnel 3. The stream of air issucked out of the cyclone through the fan 27, the throttle valve 26 andthe line 25. The granulate separated in the container 21 leaves theseparator at its bottom opening and falls on the shaking screen 28. Thematerial which falls through the shaking screen is the granulate of thedesiredgrain size and is removed through the line 29. The coarse-grainedmaterial remaining on the screen 28 is carefully comminuted in the mill30. The line 31 conveys the material issuing from the mill back into theseparator under the reduced pressure prevailing in the separator 21,where the particles of dust are separated.

The granulation may also be egected in a rotating drum. The material tobe granulated is in this case passed into the drum via a funnel and atube. There it is partly lifted from the rotating drum and forms thereina continuously moving mass. A stripper prevents the material from beinglifted too far and caking of the particles sprayed against the wall ofthe drum. The solution used for the spraying is introduced through apipe into the drum and is there converted by nozzles into radiatingsprays. The solid coating substance used for the coating is passed intothe drum through a second funnel.

The granulation process may be carried out discontinuously orcontinuously in the described apparatus.

The size of the granulates prepared by the process of the invention mayvary within very wide limits according to the existing requirements. Ingeneral, granulates of grain size over 5 mm. are only needed in specialcases. For use in washing compositions, granulates of grain size from 2down to 0.3 mm. have particular importance, while the granulates mayalso contain constituents of other grain sizes, the fraction of 2 to 0.3mm. generally constituting at least 50% by weight of the totalgranulate. In the granulate of the activator component prepared by theabove described process of the invention the organic activator ispresent substantially in the form of solid coated particles, possiblycombined with one another to give agglomerates, the nuclei of theseparticles consist of the solid activator, and these nuclei are coatedwith a layer consisting of partly hydrated salts which bind water in theform of water of crystallization and/or surfaceactive powders andpossibly film-forming colloids and/r surface-active compounds ordispersing agents. Thus in the granulates of the activator component thewater used for coating the activator in the above described granulationprocess is in practice bound by surface forces and/ or as water ofcrystallization. The coated activator particles are in this form largelyscreened from the attack of undesired reactive substances, above allagainst the moisture of the air and the water possibly in thepreparations which is not bound as water of crystallization, as well asfrom the inorganic percompounds possibly present in the preparations,especially perborate. The solid pnlverulent to granular preparationsaccording to the invention therefore also have excellent storageproperties.

It has surprisingly been found that the activity of the activator is notaffected by the water bound by surface forces and/or as water ofcrystallization. This applies especially when acylated glycolurils,especially tetraacetylglycoluril, are used as activators.

Therefore, a reaction of the organic activator with the inorganicpercompound in practice does not occur until the preparation isdissolved or dispersed in baths containing water or percompounds for thepreparation of a cold-bleaching bath.

Preparations which comprise substantially the granulated activatorcomponent, are suitable for use in the textile industry or in industriallaundries, where they are used together with hydrogen peroxide or solidpercompounds and possibly the usual additions for the preparation of thebleaching baths and bleaching washing baths.

If, in addition to the activator component according to the invention,the compositions of the invention contain other constituents usuallypresent in bleaching baths, the composition of such preparation liesapproximately in the range of the following formulation:

5% to 95%, preferably 7% to 50% by weight of an activator componentdefined above,

95% to 5%, preferably 93% to 50% by weight of neutral and/or preferablyalkaline-reacting builder salts and possibly other constituents usual inbleaching or bleaching washing compositions, such as for example,surface-active compounds, soil suspension agents, foam stabilizers,dyestuffs and perfumes and so forth.

When in the above formulation the inorganic builder salts are wholly orpartly replaced and present as percompounds yielding H 0 in aqueoussolution, the preparations according to the invention representspecially interesting bleaching compositions for practical purposes,which on dissolving in water give cold-bleaching washing liquors, inwhich the active oxygen is already effective at temperatures from 20 to70 (3., especially 30 to 60 C.

In such bleaching compositions the ratio of the activator in theactivator component of the invention to the percompound is always suchthat from 0.05 to 2 mols, preferably 0.1 to 1 mol of activator ispresent per gramatom of active oxygen of the percompound.

When such bleaching compositions contain more than 40% by weight ofactivator and percompound, this quantity relating to the pure activatorand the pure percompound without the other constituents of the activatorcomponent, these preparations are preferably used as bleaching agentconcentrates in the textile industry or in industrial laundries.

When the bleaching compositions of the invention contain up to 40% byweight of pure activator and percompound in the above-defined ratios,they are useful as bleaching washing compositions and washingassistants, which are of special practical interest and thereforerepresent a preferred field of application of the present invention. Insuch bleaching washing compositions and washing assistants, theproportions of activator and percompound constitute together mostly from5% to 40%, especially from 10% to 35% by weight of the composition. Thecomposition of such bleaching agents generally lies within the range ofthe following formulation, the constituents of the granulate of theabove-defined activator component being distributed. according to theformulation in the various categories: listed below:

5% to 40%, preferably 7% to 30% by weight of a surface active component,containing at least one surfaceactive compound of the type of thesulfonates, soaps, non-ionics, and, optionally, one or more of thefollowing substances:

0 to 10%, preferably 0.5% to 8% by weight of foam stabiilzers,

0 to 10%, preferably 0.5% to 8% by weight of nonsurface-active foaminhibitors,

5% to 40%, preferably 10% to 35% by weight of pure activator andpercompound,

10% to preferably 35% to 75% by weight of builder salts these substancesbeing preferably alkaline-reacting and the amount of these substancespreferably constituting 0.5 to 7 times, and especially 1 to 5 times, thetotal amount of surface-active compounds, and

0% to 30%, preferably 3% to 15% by weight of other bleaching and washingcomposition constituents such as, for example, soil suspension agents,textile softeners, enzymes, optical brighteners, dyestuffs and perfumes,water,

while the activator of the above-defined activator component is presentin an amount corresponding to 0.05 to 2 mols, preferably 0.1 to 1 molper gram-atom of active oxygen of the percompound.

In this general formulation are also included bleaching fine washingcompositions to be used at temperatures up to 70 C., the surface-activecompound content of which is generally in the range from 8% to 40%,preferably from to 40% by weight. Provided these fine washingcompositions are not intended for use in washing machines, especially indrum washing machines, they need not also contain foam inhibitors.Bleaching softening or after-rinsing compositions have usually asurface-active compound content of less than 5% by weight, and they alsoneed not contain foam inhibitors.

The bleaching washing compositions intended for use in washing machines,preferably in drum washing machines, are of particular practicalimportance in which the surface-active compound component constitutesusually 7% to 30% by weight; these mostly contain at least one of thefollowing two types of surface-active compound in the amounts thereindicated:

15% to 100%, preferably 35% to 90% by weight of a sulfonate and/or asulfate with preferably 8 to 18 carbon atoms in the hydrophobic residue,

10% to 60%, preferably 10% to 50% by weight of nonionics and optionallyone or more of the following substances:

% to 70%, preferably to 60% by weight of a soap,

0% to 10%, preferably 0.5% to 8% by weight of a foam stabilizer,

0% to 10%, preferably 0.5% to 8% by weight of a nonsurface-active foaminhibitor,

the foaming power, however, of the surface-active component beingreduced either by simultaneous presence of different surface-activecompounds reducing the foaming power and/or foam-inhibiting soap and/ornon-surfaceactive foam inhibitors.

The said bleaching washing compositions are generally prepared by mixingthe activator component according to the invention with washingcompositions containing percompounds, which have usually been obtainedby admixing a washing composiiton powder prepared by hot drying with apercompound. Such cold-bleaching washing compositions are marked by agood stability on storage.

The further constituents of the compositions according to the inventionare described below in more detail according to the class of substance.

The anionic, amphoteric or nonionic tensides contain in the molecule atleast one hydrophobic residue mostly containing 8 to 26, preferably 10to 22 and especially 10 to 18, carbon atoms and at least one anionicnonionic or amphoteric water-solubilizing group. The preferablysaturated hydrophobic residue is mostly aliphatic, but

possibly also alicyclic in nature. It may be combined directly with thewater-solubilizing group or through intermediate members. Suitableintermediate members are, for example, benzene rings, carboxylic acidester or carboxylic acid amide groups, residues of polyhydric alcoholslinked in ether or ester-like form, such as, for example, those ofethylene glycol, propylene glycol, glycerine or corresponding polyetherresidues.

The hydrophobic residue is preferably an aliphatic hydrocarbon residuewith 0 to 18, preferably 12 to 18, carbon atoms but deviations from thepreferred range of carbon atoms are possible, depending on the nature ofthe surface-active compound in question.

Soaps from natural or synthetic fatty acids, possibly also from resin ornaphthenic acids, are utilizable as anionic detergent substances,especially when these acids have iodine values of not more than 30, andpreferably of less than 10.

Of the synthetic anionic surface-active compounds, the sulfonates andsulfates possess special practical importance.

The sulfonates include, for example, the alkylaryl sulfonates,especially alkylbenzene sulfonates, which are obtained from preferablystraight-chain aliphatic hydrocarbons having 9 to 15, especially 10 to14 carbon atoms, by chlorinating and alkylating benzene or fromcorresponding terminal or non-terminal olefins by alkylation of benzeneand sulfonation of the alkylbenzenes obtained. Further, aliphaticsulfonates are of interest, such as are obtainable, for example, frompreferably saturated hydrocarbons containing 8 to 18 and preferably 12to 18 carbon atoms in the molecule by sulfochlorination with sulfurdioxide and chlorine or sulfoxidation with sulfur dioxide and oxygen,and conversion of the products thereby obtained into the sulfonates. Asaliphatic sulfonates, mixtures containing alkene sulfonates,hydroxyalkane sulfonates and disulfonates are useful, which are obtainedfrom terminal or non-terminal C and preferably C1248 olefins bysulfonation with sulfur trioxide and acid or alkaline hydrolysis of thesulfonation products. In the aliphatic sulfonates thus prepared, thesulfonate group is frequently found attached to a secondary carbon atom;however, sulfonates with a terminal sulfonate group obtained by reactionof terminal olefins with bisufite can also be used.

Furthermore, salts, preferably dialkali metal salts of ozsulfo-fattyacids, and salts of esters of these acids with monoor poly-hydricalcohol containing 1 to 4, and preferably 1 to 2 carbon atoms belong tothe sulfonates to be used according to the invention.

Further useful sulfonates are salts of fatty acid esters ofhydroxyethanesulfonic acid or dihydroxypropane sulfonic acid, the saltsof the fatty alcohol esters of lower aliphatic or aromatic sulfomonoordi-carboxylic acids containing 1 to 8 carbon atoms, alkylglycerylethersulfonates and the salts of the amide-like condensation products offatty acids or sulfonic acids with aminoethanesulfonic acid.

As tensides of the sulfate type are fatty alcohol sulfates, especiallythose prepared from coconut fat alcohols, tallow fat alcohols or oleylalcohol. Useful sulfonation products of the sulfate type are alsoobtainable from terminal or non-terminal C olefins. Sulfated fatty acidalkylolamides or fatty acid monoglycerides, and sulfated alkoxylationproducts of alkylphenols (C alkyl), fatty alcohols, fatty acid amides orfatty acid alkylolamides, which may contain in the molecule 0.5 to 20,preferably 1 to 8 and especially 2 to 4 ethylene and/ or propyleneglycol resi dues, also belong to this group of surface-active compounds.

Suitable anionic surface-active compounds of the carboxylate type arethe fatty acid esters or fatty alcohol ethers of hydroxycarboxylicacids, and the amide-like condensation products of fatty acids orsulfonic acids with aminocarboxylic acids, for example, with glycocoll,sarcosin or protein hydrolysates.

The nonionic surface-active compounds, here called nonionics, for thesake of simplicity, include products which owe their solubility in waterto the presence of polyether chains, amineoxide, sulfoxide orphosphineoxide groups, alkylolamide groups and very generally, to anaccumulation of hydroxyl groups.

The products obtainable by addition of ethylene oxide and/ or glycide tofatty alcohols, alkylphenols, fatty acids, fatty amines, fatty acid andsulfonic acid amides are of special practical interest. These non-ionicsmay contain per molecule 4 to 100, preferably 6 to 40 and especially 8to 20 ether residues, particularly ethylene glycol ether residues.Moreover, propylene or butylene glycol ether residues or polyetherchains may be present in or at the ends of these polyether residues.

Further, products known by the trade name of Pluronics or Tetronicsbelong to the nonionics. They are obtained from Water-insolublepolypropylene glycols or from water-insoluble propoxylated loweraliphatic alcohols containing 1 to 8, preferably 3 to 6 carbon atomsand/or from water-insoluble propoxylated alkylenediamines. Thesewater-insoluble (i.e. hydrophobic) propylene oxide derivatives areconverted into the said nonionics by ethoxylation until they becomesoluble in water. Finally, the reaction products of the above-mentionedaliphatic alcohols with propylene oxide known as Ucon- Fluid some ofwhich are still water-soluble, are useful as nonionics.

The nonionics also include fatty acid or sulfonic acid alkylolamideswhich are derived, for example, from monoor di-ethanolamine,dihydroxypropylamine or other polyhydroxyalkylamines, for example theglycamines. They can be replaced by amides from higher primary orsecondary alkylamines and polyhydroxycarboxylic acids.

The surface-active amineoxides include, for example, the productsderived from higher tertiary amines having a hydrophobic alkyl residueand two shorter alkyl and/or alkylol residues containing up to 4 carbonatoms each.

Suitable as nonionic dispersing agents are possibly nonsurface-activewater-soluble compounds or compounds emulsifiable or dispersible inwater, such as, for example, fatty acid partial glycerides and alsocompounds which do, not contain hydrophobic residues within the meaningof the above-described surface-active compounds, as for example, solidor liquid polyethylene glycols, ethylene oxide adducts of glycerine andother polyalcohols.

Amphoteric surface-active compounds contain the molecule both acid andbasic hydrophilic groups. Carboxyl, sulfonic acid, sulfuric acid halfester, phosphonic acid and phosphoric acid partial ester groups are theacid groups. Basic groups include primary, secondary, tertiary andquaternary ammonium groups. Amphoteric compounds with quaternaryammonium groups belong to the betaine type.

Carboxy, sulfate and sulfonate betaines have particular practicalinterest on account of their good compatibility with othersurface-active compounds. Suitable sulfobetaines are obtained, forexample, by reacting tertiary amines containing at least one hydrophobicalkyl residue with sultones, for example, propaneor butane-sultone.Corresponding carboxybetaines are obtained by reacting the said tertiaryamines with chloroacetic acid, or its salts or with chloroacetic acidesters and splitting the ester linkage.

The foaming power of the surface-active compounds can be increased orreduced by combination of suitable types of surface-active compounds,just as it can be changed by additions of non-surface-active organicsubstances.

Suitable foam stabilizers, above all in the case of surface-activecompounds of the sulfonate or sulfate type, are surface-active carboxyor sulfo-betaines and also the above-mentioned non-ionics of thealkylolamide type. Moreover, fatty alcohols or higher terminal diols canbe utilized for this purpose.

Products with a reduced foaming power are primarily intended for use inwashing-and dishwashing machines, where sometimes a limited repressionof foam is sufiicient while in other cases a stronger foam repressionmay be desired. Products which foam in the middle range of temperatureup to about 65 C. but at higher temperatures (70 C. to 100 C.) developless and less foam, are of special practical importance.

A reduced foaming power is frequently obtained with combinations ofdifferent types of surface-active compounds, especially withcombinations of synthetic anionic surface-active compounds, particularlyof (1) sulfates and/or sulfonates or of (2) nonionics on the one handand (3) soaps on the other hand. With combinations of the components (1)and (2) or (1), (2) and (3), the foaming power can be affected by theparticular soap used. The inhibition of foam is smaller with soaps frompreferably saturated fatty acids with 12 to 18 carbon atoms, while agreater inhibition of foaming, particularly in the higher temperaturerange, is obtained by soaps from saturated fatty acid mixtures having 20to 26, preferably 20 to 22 carbon atoms, used in an amount of from atleast 5%, preferably at least by weight of the total soap fractionpresent in the combination of surface-active compounds.

The foaming power of the surface-active compounds can also be reduced,by the addition of known, non-surface-active foam inhibitors. Theseinclude optionally chlorine-containing N-alkylated aminotriazines, whichare obtained by reacting 1 mol of cyanuric cloride with 2 to 3 mols of amonoand/or di-alkylamine having 6 to 20, preferably 8 to 18 carbon atomsin the alkyl residue. Aminotriazine or melamine derivatives whichcontain propylene glycol or butylene glycol ether chains, in an amountof 10 to 100 of such glycol residues per molecule, have a similaraction. Such compounds are obtained, for example, by addition ofcorresponding amounts of propylene and/or butylene oxide toaminotriazine, especially to melamine. The reaction products from 1 molof melamine with at least 20 mol of propylene oxide or at least 10 molof butylene oxide are preferred. Products which are obtained by additionof 5 to 10 mol of propylene oxide to 1 mol of melamine and furtheraddition of 10 to 50 mol of butylene oxide to this propylene oxidederivative have proved particularly effective.

Other non-surface-active water-insoluble organic compounds, such asparafiins or halogenated paraffins with melting points below C.,aliphatic C to C ketones and aliphatic carboxylic acid esters, whichcontain at least 18 carbon atoms in the acid or alcohol residue,possibly also in both of these two residues (for example triglyceridesor fatty acid-fatty alcohol esters), can be used as foam inhibitors,particularly in combinations of anionic synthetic surface-activecompounds and soaps.

The non-surface-active foam inhiibtors are frequently only completelyeffective at temperatures at which they are present in the liquid state,so that the foaming behavior of the products can be controlled by choiceof suitable foam inhibitors in a similar way to that by the choice ofsoaps from fatty acids of suitable chain lengths.

When foam stabilizers are combined with foam inhibitors dependent upontemperature, good foaming products are obtained at lower temperatureswhich, as the temperature approaches the boiling temperature, foam lessand less.

Suitable Weakly-foaming nonionics, which can be used both alone and incombination with anionic, amphoteric and nonionic surface-activecompounds and which reduce the foaming power of more strongly foamingsurfaceactive compounds, are products of addition of propylene oxide tothe above-described surface-active polyethylene glycol ethers as well asthe also above-described Pluronic, Tetronic and Ucon-Fluid types.

Suitable builders are weakly acid, neutral and alkaline reactinginorganic or organic salts, especially inorganic or organiccomplex-foaming substances.

Useful, weakly acid, neutral or alkaline-reacting salts according to theinvention are, for example, the alkali metal bicarbonates, carbonates,borates or silicates, mono-, dior tri-alkali metal orthophosphates, diortetraalkali metal pyrophosphates, alkali metal metaphosphates known ascomplex-forming substances, alkali metal sulfates and the alkali metalsalts of organic, non-surfaceactive sulfonic acids, carboxylic acids andsulfocarboxylic acids containing 1 to 8 carbon atoms. These include, forexample, water-soluble salts of benzene-, tolueneor xylene-sulfonicacid, water-soluble salts of sulfoacetic acid, sulfobenzoic acid orsalts of sulfodicarboxylic acids and the salts of acetic acid, lacticacid, citric acid and tartaric acid.

Further, the water soluble salts of higher molecular weightpolycarboxylic acids are utilizable as builders, especiallypolymerizates of maleic acid, itaconic acid, mesaconic, fumaric acid,aconitic acid, methylenemalonic acid and citraconic acid.Copolymerizates of these acids With one another or with otherpolymerizable substances, as for example, with ethylene, propylene,acrylic acid, methacrylic acid, crotonic acid, 3 butenecarboxylic acid,3- methyl 3 butenecarboxylic acid and with vinyl methyl ether, vinylacetate, isobutylene, acrylamide and styrene, are utilizable.

Suitable complex-forming builders are also the weakly acid reactingmetaphosphates and the alkaline reacting polyphosphates, especiallytripolyphosphate, in the form of their alkali metal salts. They may bewholly or partly replaced by organic complex forming substances.

The organic complex-forming substances include, for example,nitrilotriacetic acid, ethylenediaminetetraacetic acid, N hydroxyethylethylenediaminetriacetic acid, polyalkylene-polyamine-N-polycarboxylicacids and other known organic complex-forming substances, whilecombinations of diiferent complex-forming substances may a 15 also be'used. Diand poly-phosphonic acids of the following constitutions alsobelong to the other known complex-forming substances:

OH X OH OH X OH I X OH Germain. o=l .t l=o N t l=o] dnfrn dnzn irbnr XOH HO X X OH N: auto] assists [she] 14... Hit. M14...

in which R represents alkyl and R alkylene radicals with l to 8,preferably 1 to 4 carbon atoms, X and Y represent hydrogen or alkylradicals with l to 4 carbon atoms and Z represents --OH, ---NH; or NXR.For a practical application above all the following compounds areconsidered: methylenedisphosphonic acid, l-hydroxyethane-1,1-diphosphonic acid, l-aminoethane-1,1-diphosphonic acid,amino-tri-(methylenephosphonic acid), methylaminoorethyla-mino-di-((methylenephosphonic acid as well as ethylenediaminetetra (methylenephosphonic acid). All these complexing compounds may bepresent as free acids or preferably as the alkali metal salts.

Further, soil suspending agents or greying inhibitors may be containedin the preparations according to the invention, which hold the dirtloosened from the fiber suspended in the bath and thus prevent greying.Watersoluble colloids of mostly organic nature are suitable for thispurpose, for example, the water-soluble salts of polymeric carboxylicacids, glue, gelatine, salts of ether-carboxylic acids or ether-sulfonicacids of starch or cellulose or salts of acid sulfuric acid esters ofcellulose or starch. Water-soluble polyamides containing acid groups arealso suitable for this purpose. Furthermore, soluble starch preparationsand starch products other than those mentioned above can be used, forexample, degraded starch, and aldehyde starches. Polyvinylpyrrolidone isalso useful.

The constituents of the treatment compositions according to theinvention, especially washing compositions and washing assistants ofthis kind, and particularly the builder substances, are usually chosenso that the preparations have a neutral to distinctly alkaline reaction,so that the pH value of a 1% solution of the preparations mostly lie inthe region from 7 to 12. Fine washing compositions usually have aneutral to weakly alkaline reaction (pH value 7 to 9.5, while soaking,prewashing and boiling washing compositions are adjusted to be morestrongly alkaline (pH value 9.5 to 12, preferably 10 to 11.5). Theaction of the activators is combined with a certain consumption ofalkali. Therefore, the builder substances present should be in an amountsufficient to prevent the pH value from falling below the given minimumvalues during the whole period of treatment.

Of the, preferably inorganic, per-compounds yielding H in aqueoussolution, sodium perboate tetrahydrate (NaBO- .H O .3H O) is of specialpractical importance. Partly or completely dehydrated perborates, i.e.,up to NaBO .H O may be used in its place. Borates such as NaBO .H Odescribed in German Pat. 901,287 and US. Pat. 2,491,789, in which theratio Na O:B 0 is less than than 0.5 :1 and preferably lies in theregion of 0.4 to 0.15:1, while the ratio H O :Na lies in the region of0.5 to 4:1 are also useful. All these perborates may be wholly or partlyreplaced by other inorganic per-compounds, especially by peroxyhydrates,such as the peroxyhydrates of ortho-, pyroor polyphosphates, especiallyof the tripolyphosphates, as well as the carbonates.

It is advisable to incorporate in the compositions from 0.25% to byweight of the usual water-soluble and/ or water-insoluble stabilizersfor the stabilization of the pre-compounds. Suitable water-insolubleper-compound stabilizers which, for example, constitute 1% to 8%,preferably 2% to 7%, of the weight of the total preparation, are themagnesium silicates (MgO:SiO =4"to 1:4,

preferably 2:1 to 1:2 and especially 1:1), mostly obtained byprecipitation from aqueous solutions. Other alkaline earth metal,cadmium or tin silicates of corresponding composition are utilizable intheir place. Water-contain ing tin oxides are also suitable asstabilizers. Watersoluble stabilizers, which may be present togetherwith water-insoluble stabilizers, are the organic complexformingsubstances the amount of which may constitute 0.25% 'to 5%, preferably0.5% to 2.5% of the weight of the whole preparation. l

The enzymes to be used are mostly a mixture of different enzymicsubstances. They are called proteases, amylases, carbohydrases,esterases, lipases, oxidoreductases, catalases, peroxidases, ureases,isomerases, layases, transferases, desmolases or nucleases, dependingupon their action. The enzymic substances obtained from strains ofbacteria or fungi such as Bacillus subtilis and Streptomyes griseus areof particular interest, especially proteases or amylases. Preparationsobtained from Bacillus subtilis have the advantage compared with othersthat they are relatively stable towards alkali, per-compounds andanionic detergent substances and are still active at temperatures up to70 C. l I

Enzyme preparations are usually marketed by the manufacturers as aqueoussolutions of the active substances or with the addition of diluents, aspowders. Suitable diluents are sodium sulfate, sodium chloride, alkalimetal or'tho-, pyroor polyphosphates, especially tripolyphosphate.Frequently moist enzyme preparationsare mixed with calcined salts, whichthen bind Water of crystallization present and the enzymic substance,possibly with agglomeration of the particles to larger particles.

When the enzymic substances are present as dry powders, liquid,paste-like and possibly also solid, nonionic, preferably surface-active,organic compounds especially the above-described non-ionics, can be usedat the usual room temperatures to bind the enzymes to the powders of thewashing compositions or washing assistants. For this purpose a mixtureof the respectiveproduct and the enzymic substance is preferably sprayedwith the abovementioned nonionic substances, or the enzyme preparationsis dispersed in the said nonionic substance and this dispersion isunited with the other constituents of the product. When these otherconstituents are solids, the dispersion of the enzymic substances in thenon-ionic component can also be sprayed on the other solid constituents.

The enzymes, or combinations of enzymes with different actions, aregenerally used in quantities such that the finished products haveprotease activities of 50 to 5000, preferably to 2500 LVE/ g. and/oramylases activities of 20 to 5000, preferably 50 to 2000 SKBE/g. and/orlipase activities of 2 to 1000, preferably 5 to 500 IE/g.

These data on enzyme activities result from the activities of thoseenzyme preparations which at the present time seem to be suitable fromthe economic standpoint for use in the washing composition field. Fromthe chemical-technical standpoint the enzyme activities of thepreparations can be increased as desired, so that the activities in thecase of proteases and amylases may be raised, for example, up to fivetimes, and in the case of lipases, for example, up to ten times, thehighest values given above. If, therefore, in the future preparationswith such high activities should be available which also economicallyappear appropriate for the use in the application fields, named at thebeginning, products with respective higher enzyme activities can beprepared.

With reference to the determination of the enzyme activities, thefollowing literature references are given: Determination of the activityof proteases according to Lohlein-Volhardz A. Kunzel, Chemical TanningPocketbook, 6th ed., Dresden and Leipzig, 1955; determination of theactivity of amylases: J. Wohlgemuth, Biochemische Zeitschrift, vol. 9,(1908), pp. 1-9; R. M. Sandstedt et 'al., Cereal'Chemistry, vol. 16,(1939), pp. 712-723; deter- 17 mination of the activity oflipases: R.Willst'atter et al., Hoppe-Seylers Zeitschrift fiir PhysiologicheChemie, vol. 125 (1923), pp. 110-117; R. Boissonas, Helvetica ChimicaActa, vol. 31 (1948), pp. 1571-1576.

The products according to the invention may also contain antimicrobialsubstances. As such, the 2-hydroxy- 2',4,4-trichloro-diphenylether hasbeen proven good.

Particularly import representative of optical brighteners are thediaminostilbene sulfonic acid derivatives of the general formula J ll 1'1 N N n o a Rn H S og 03 H R:

wherein R and R may represent halogen atoms, lower alkoxy groups,theamino group or radicals of aliphatic, aromatic or heterocyclicprimary or secondary amines as well as radicals of aminosulfonic acidswhere the aliphatic radicals, present in the above groups, containpreferably 1 to 4, and particularly 2 to 4 carbonatoms, while theheterocyclic ring systems are primarily rings with 5 or 6 members. Asaromatic amine radicals preferably aniline, anthranilic acid oranilinesulfonic acid are of interest. Brighteners derived from thediaminostilbene sulfonic acids are mostly used as brighteners forcotton. The following products, derived from Formula I, are commerciallyavailable, where R represents the residue morpholino-, -NH--C H NHC H SOH, --OCH Some of the brighteners are, in regard to their fiber afiinity,to be considered as transitional types to the polyamide brighteners,such as thebrightener with R -NH-C H To the cotton brighteners of thediaminostilbene sulfonicacid type also belongs the compound4,4-bis-(4-phenyl vicinal-triazolyl-2) stil'bene disulfonic acid-2,2.

These optical brighteners are present in the products of the invention,particularly in the washing agents, according to the invention,generally in amounts of from 0.05% to 1.5%, preferably from 0.07% to 1%by weight.

The present invention will be further described with reference to thefollowing specific examples which are not to be deemed limitative of theinvention.

EXAMPLES Examples V1 to V3 describe the preparation of the activatorcomponent according to the invention.

Example V1 An apparatus illustrated in FIG. 1 with a granulating discserved for carrying out the process. 50 kg./hr. of

tetraacetylglycoluril of a particle size range between 0.08 and 0.2 mm.and 70 kg./hr. of calcined sodium tripolyphosphate of substantially thesame particle size range were passed on to the granulating disc, thesize, inclination and speed of rotation of which were such that theaverage duration of the mixture thereon was 60 to 80 seconds. 15 kg./hr.of a solution of sodium tripolyphosphate saturated at room temperaturewere sprayed by means of a nozzle on the activator-tripolyphosphatemixture. The finished granulate was allowed to flow for 5 secondsthrough a countercurrent of air at a temperature of about 15 C. The"activator component thus obtained had a particle size range in theregion of 0.3 to 2.5 mm. I

1 8 Example V2 25 kg./hr. of tetraacetylglycoluril, of a particle sizerange of 0.08 to 0.2 mm., were sprayed in a rotating drum with 60kg./hr. of a hot 10% aqueous gelatine solution in the first third of thelength of the drum. 50 kg./hr. of calcined sodium tripolyphosphate of aparticle size range of 0.1 to 2.2 mm. were fed into the last third ofthe drum, and the average duration of time of the activator in the drumwas to 100 seconds. The granulate thus obtained, after running through acountercurrent stream of air at 22 C. had a particle size range ofbetween 0.3 and 3.5 mm.

Example V3 1.5 kg. of tetraacetylglycoluril, particle size range of 0.08to 0.2 mm., was placed in a rotating drum and sprayed with 0.8 kg. of a5% carboxymethylcellulose solution, in a discontinuous operation. 1.7kg. of magnesium oxide, particle size range of 0.008 to 0.12 mm., wasadded to this mixture in a period of 15 minutes and the mixing wascontinued for a further 15 minutes. The granulate obtained had aparticle size range in the region of 0.2 to 3 mm.

Example M1 7 To determine the stability on storage of the preparationsaccording to the invention, a bleaching agent of the followingcomposition was prepared.

80% by weight of an activator component consisting of:

25% by weight of tetraacetylglycoluril, 5% by weight of gelatine, 50% byweight of sodium tripolyphosphate, 20% by weight of water and 20% byweight of sodium perborate tetrahydrate.

TABLE I Residual perborate content in percent after- 10 days 30 days 50days Bleaching agent Example M1 98 32 Sample for comparison 57 16 2 Theperborate content of the test samples were determined by the followingmethod:

In each case 100 g. of the samples were added to about 0.5 liters of 10%sulfuric acid in a 1-liter measuring flask. After dissolution had takenplace, the flask was filled up to the calibration mark with 10% sulfuricacid. 10 ml. of this solution were removed, treated with about 10 ml. ofa 10% potassium iodide solution and, after addition of a few drops of asaturated solution of ammonium molybdate, titrated with 0.1 N sodiumthiosulfate solution until a light yellow coloration was obtained. Thena few drops of a starch solution were added and the solution was furthertitrated until decolorization occurred. The residual perborate was thendetermined according to the following formula Residual perborate contentin percent [m1. 0.1 N thiosulfate]-0.77-l00 Init,ial perborate contentin percent 19 agent according to the invention has a distinctly betterstability on storage.

The following specific examples describe the composition of furtherpreparations of the invention. The saltlike constituents containedtherein such as salt-like surface-active compounds, other organic saltsas well as inorganic salts are present as sodium salts, if not expresslystated otherwise. The other terms and abbreviations used have thefollowing meanings:

ABS is the salt of an alkylbenzenesulfonic acid with 10 to 15,essentially 11 to 13 carbon atoms in the alkyl chain obtained bycondensing straight-chain olefins with benzene and sulfonation of thealkylbenzene thus formed.

Alkanesulfonate is a sulfonate obtained from paraffins with 12 to 16carbon atoms via the sulfoxidation method. 1 Fs-estersulfonate is asulfonate obtained from the methyl ester of a hardened tallow fatty acidby sulfonation with S Olefinsulfonate is a sulfonate obtained frommixtures of olefins with 13 to 18 carbon atoms by sulfonation with S0and hydrolysis of the sulfonation product with alkaline liquor, whichsulfonate consists substantially of alkanesulfonate andhydroxyalkanesulfonate, but in addition still contains small amounts ofdisulfonates. Each olefinsulfonate-containing preparation was preparedwith use of two diiferent types of olefinsulfonate; one was preparedfrom a mixture of straight-chain terminal olefins, and the other from amixture of nonterminal olefins.

KA-Sulfate and TA-Sulfate are the salts of sulfated substantiallysaturated fatty alcohols prepared by reduction of coconut fatty acid andtallow fatty acid respectively.

KA-EO-Sulfate," TA-EO-Sulfate and OA-EO-Sulfate are the sulfatedproducts of addition of 2 mols of ethylene oxide to 1 mol of coconutfatty alcohol, of 3 mols of ethylene oxide to 1 mol of tallow fattyalcohol and of 2 mols of ethylene oxide to 1 mol of oleyl alcoholrespectively.

are the products of addition of ethylene oxide (E0) and propylene oxide(PO) to commercial oleyl alcohol (0A), and coconut alcohol (KA).

Perborate is a product containing about of active oxygen of theapproximate composition NTA, EDTA and HEDP are the salts ofnitrilotriacetic acid, ethylenediaminetetraacetic acid and bydroxyethanediphosphonic acid respectively.

Soap A or B is a soap prepared from a fatty acid mixture of 9% by wt. C14% by wt. C and 77% by wt. C (iodine value 3) (A); or 8% by wt. C 32%by wt. C 12% by wt. C and 48% by wt. C (iodine value 4) (B).

CMC is the salt of carboxymethylcellulose.

In theexamples a mixture of about 45% of a-N,N'-di-(alkylamino)-monochlorotriazine and about 55% of aN,N',N"-tri(alkylamino) -triazine was used as non-surfaceactive foaminhibitor. The alkyl residues in these triazine 4 derivatives arepresent as a mixture of homologswith 8 to 18 carbon atoms. Themonochlorotriazine derivative or thhe trialkylaminotriazine could beused with a similar result. If the products described contain syntheticsulfates or sulfonates together with soap, the other non-surfaceactivefoam inhibitors mentioned in the description may be used, for exampleparaflin oil or paraflin. In the production of the preparations thenon-surface-active foam inhibitor dissolved in a suitable organicsolvent or in molten state was sprayed by means of a nozzle on themoving pulverulent preparation.

In all the examples the amounts relates to the pure substances. Thesesubstances may contain impurities caused 20 a by the preparation suchas, for example, water, sodium sulfate, sodium chloride, sodiumcarbonate, etc. Thus in the subsequent Table II, the sign in the line NaSO means that small amounts of sodium sulfate are present as impurity inthe anionic surface-active compounds. Since such impurities do notimpair the activity of the individual substances, they are not mentionedin the formulations. The expression residue therefore stands essentiallyfor water and the above mentioned salts as well as for dyestuffs andperfiurmes.

Example M2 Bleaching activatorfor industrial laundries:

80.0% by weight of an activator component compris- 25% by weighttetraacetylglycoluril 6% by weight of gelatine 1 50% by weight sodiumtripolyphosphate 19% by weight water 5.0% by weight Na O:3.3SiO

3.5% by weight OA-l-lO E0 2.5% by weight ABS Remainder sodium sulfateand water.

Example M3 Bleaching agent concentrate:

' 70.0% by weight of an activator component compris- 30% by weighttetraacetylglycoluril 5% by weight OA+5 E0 50% by weight sodiumtripolyphosphate 15% by weight water 30.0% by weight perborate.

I I Example M4 Bleaching prewashing agent: 7

The following Examples M5 to M10 set forth in Table II describebleaching washing compositions according to the invention, in which thefollowing activator components prepared according to Examples used:

Activator component V1:

37.5% by weighttetraacetylglycoluril 55.0% by weight sodiumtripolyphosphate 7.5% by weight water Activator component V2:

. 25% by weight tetraacetylglycoluril 6% by weight gelatine 50% byweight sodium tripolyphosphate 19% by weight water. J I l .Activatorcomponent V3:

" 37.5 by weight tetraacetylglycoluril 1.0% by weight CMC 42.5% byweight magnesium oxide 19.0% by weight water,

V1, V2 and V3 were.

TABLE H 1 wherein R here and hereafter is a member selected from thegroup consisting of methyl, ethyl, n-propyl, Percent fg f i flisopropyl, phenyl, tolyl, xylyl and chloroalkyl having 1 to 3 carbonatoms and X represents a member Components of the preparation M5 M6 M7M8 M9 M10 5 selected from the group consisting of ABS- 3.0Alkanesulionate 4. 5 5. 5 Fs-estersulfonate. 2. 5 G 0-R C 0-3. 0 OROlefinsulfonate. 5.4 6.0 KA-sulfate-.- 2 0 R, .CH:-N- v -CH2CHz-N and -NC O-R C O-R C OR (b) N-alkyl-N-sulfonyl-carbonamides having the formulazr-N S0R.flj

wherein R represents alkyl having 1 to 3 carbon atoms, R represents amember selected from the group consisting of R, p-nitrophenyl andp-methoxyphenyl and R represents R,

(c) N-acyl-hydantoins having the formula Ere CMC Y3 Brightener.Remainder wate C 0-( )'Y Xsz-IL' N-Xu N Instead of the activatorcomponents used in the washing A compositions of Table II, those inwhich the tetraacetylglycoluril is replaced by other glycolurils ofFormula X or by activators of Formulae I to 1X may also be used withwherein at least one of X and X is RC0 and the a imilar result, 35 otheris selected from the group consisting of RCO,

Cotton brighteners, polyamide brighteners, polyester R, carboxymethyland carbethoxymethyl, and Y brighteners and their combinations may beused as optical and Y32 are selected from the group consisting ofbrighteners, depending upon the purpose for which the hydrogen and alkylhaving 1 to 2 carbon atoms, washing composition according to theinvention is to be (d)"cyclic-N-acyl-hydrazines having the formula used.a

In preparations containing enzymesare to be made, 7 to N 15% by weightof commercial products are used which, Where solid enzyme concentratesare concerned, are adhr-COR justed by the manufacturer to the followingactivities by addition of inorganic salts, mostly sodium sulfate orsowherein the two nitrogen atoms are part of a hetero dmmtripolyphosphate: 1 ring selected from the group consisting of maleic Aprotease with 125,000 DIE/g hydrazide, phthalic hydrazide, triazole andurazole,

An amylase with 75,000 SKBE/g (e) carbonic esters having the formula Alipase with 10,000 IE/ g.

The PrFceding R are fllustratlve of wherein X represents anelectron-attracting radical the practice of the invention. It is to beunderstood, howl ted from the group consisting of p-carboxyever, thatother expedients known to those skllled 1n the phenyl, p sulfophenyl,and ethoxycarbonyl, art or disclo herein y 13% p y Without p (f)pyrocarbonic acid esters of alkanols having 1 to 4 ing from the spiritof the invention or the scope of the 5 carbon atoms, appended claims.(g) triacyl-cyanurates having the formula We claim:

1. A solid, pulverulent to granular activator compo- A V nent useful inthe preparation of aqueous cold-bleaching 1 r I baths, said activatorcomponent being a granulate at least 50% of which has a particle sizefraction of between 0.3

mm. and 2 mm., consisting of an activator for active oxygen derived fromacompounds yielding H 0 in aquem ous solution, said activator having amelting point of at 1 V N least C. and an activating action of at least3 in the Per-Acid Formation Test and is selected from the groupconsisting of (a) N-diacylated amines having the formula a wherein R-hasthe above-defined values, '(h) 0,N,N -trisubstituted hydroxylamineshaving the formula 23 7 wherein R represents a member selected from thegroup consisting of R and and the CO, succinyl and phthalyl, and nrepresents an integer from to 2, (i) N,N-diacyl-sulfurylamides havingthe formula wherein R and R represent alkyl having 1 to 3 carbon atomsand R and R represent alkyl having 1 to 4 carbon atoms and phenyl,

(j) 1,3-diacyl-4,S-diacyloxy-imidazolidines having the formula wherein Xrepresents a member selected from the group consisting of R andhydrogen, and

(k) acylated glycolurils having the formula glycolurils having theformula wherein X represents a member selected from the group consistingof R-CO and R, I said activator being in the form of particlessubstantially surrounded with an at least water-dispersible coatingsubstance inert to said activator and capable of binding water by forcesselected from the group consisting of surface forces and water ofcrystallization, said coating substance containing bound water and beingselected from the group consisting of (i) calcined water-solubleinorganic salts which are able to crystallize with the binding of waterof crystallization, with a degree of hydration of from 5% to 90% of thehighest possible hydration for the solid stable hydrate and (ii)water-insoluble inorganic and organic pulverulent materials with a largesurface area selected from the group consisting of microcrystallinesilicic acid, magnesium oxide, magnesium silicate, tin oxide, tinsilicate, titanium dioxde, polyethylene powder and polypropylene powder,saidactivator constituting from 5% to 50% by weight and said coatingsubstance constituting from 50% to 95% by weight, of the activatorcomponent.

2. The composition of claim 1 wherein said activator constitutes from to40% by weight and said coating substance constitutes from 60% to 85% byweight of the activator component composition.

3. The compositionof claim 1 wherein said activator has an activatingaction of at least 4.5 in the Per-Acid Formation Test.

4. The composition of claim 1 wherein said at least water-dispersiblecoating substance has a'further content of from 1% to 20% by weight ofthe total activator component composition of at least one agglomerationagent selected from the group consisting of water-soluble towater-dispersible cellulose, protein and starch derivatives,water-soluble alkali metal silicates, surface-active compounds,surface-active dispersing agents and said bound water.

5. The composition of claim 1 consisting essentially of from 15 %'to 40%by weight of said activator, from 35% to 85 of a water-soluble saltcapable of binding water as water of crystallization and being from 5%to 95% hydrated and from 0% to 15% by weight of an agglomeration agentforming with water a solution to dispersion suitable for wetting saidactivator.

6. The composition of claim 1 consisting essentially of from 15% to 40%by weight of said activator, from 25% to 82% by weight of awater-insoluble inorganic or organic pulverulent compound having a largesurface area, from 2% to 20% of water bound by surface forces and from0% to 20% by weight of an agglomeration agent forming with water asolution to dispersion suitable for wettingsaid activator. V v

7. The composition of claim 1 wherein said activator for active oxygenhas the formula wherein R R and R represent a member selected from thegroup consisting of alkyl having 1 to 3 carbon atoms, phenyl, andphenylalkyl having 7 to 8 carbon atoms and X represents a memberselected from the group consisting of R and R -CO.

8. The composition of claim 5 whereinsaid activator istetraacetylglycoluril and said water-soluble salt is sodiumtripolyphosphate.

9. The composition of claim 5 wherein said activator istetraacetylglycoluril, said water-soluble salt is sodiumtripolyphosphate and said agglomeration agent is present in an amount offrom 1% to 10% by weight and is gelatine.

. 10. The composition of claim 6 wherein said activator istetraacetylglycoluril, said water-insoluble pulverulent compound havinga large surface is magnesium oxide and said agglomeration agent ispresent in an amount of from 1% to 10% by weight and iscarboxymethylcellulose.

11. The composition of claim 7 wherein said activator for active oxygenis a member selected from the group consisting of tetraacetylglycoluril,tetrapropionylglycoluril, methyltriacetylglycolurilanddiacetyldibenzoylglycoluril.

12. A process for the production of solid, pulverulent to granularactivator component useful in the preparation of aqueous cold-bleachingbaths, said activator component being a granulate at least 50% of whichhas a particle size fraction between 0.3 mm. and 2 mm., consisting of,in any sequence, wetting a solid, pulverulent to granular activator, foractive oxygen derived from compounds yielding H 0 in aqueous solution asclaimed in claim 1, with an aqueous liquid and admixing an at leastwaterdispersible solid pulverulent coating substance inert to forcesselected from the group consisting of surface forces and water ofcrystallization, selected from the group consisting of (i) calcinedwater-soluble inorganic salts which are able to crystallize with thebinding of water of crystallization and (ii) water-insoluble inorganicand organic pulverulent materials with a large surface area selectedfrom the group consisting of microcrystalline silicic acid, magnesiumoxide, magnesium silicate, tin oxide, tin silicatc, titanium dioxide,polyethylene powder and polypropylene powder, the relative proportionsof said activator, said aqueous liquid and said solid coating substancebeing selected so that the water present is bound by forces selectedfrom the group consisting of surface forces and water of crystallizationand said activator constitutes from 5% to 50% by weight and said coatingsubstance including bound water constitutes from 50% to 95% by weight,of the activator component.

References Cited UNITED STATES PATENTS Moyer et al 252-99 Disch et a1.252-99 XR Derangeon et al. 25299 XR Corey et al. 252-99 Chase 25299Maruta et a1 252-99 Cray 25299 Woods 252-99 XR MAYER WEINBLATT, PrimaryExaminer U.S. CI. XLR.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 5,789,002 Jan. 29,197

Patent No. Dated lnv Rudolf Weber et a1.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

lat t. 9 1- 5:22:

1 #7 Change "555st" to Twists" 3 2 Change "mol/liter" to :nMol/liter 3 6Change "(j)" to (l) I 9 l Change" "egected". to effected 39 After"sulfonate's; please insert su-lfates,

21 "In" should be If i 3 Delete the phrase glycolurlls having theformula" which was repeated in error. 7 i

l6 86 In original claim 7, now known as claim .5, delete l7 the words"and being from 5% to 95% hydrated".

This was cancelled as per Amendment Rule 116.

2 22 In original claim l0, 'now' known as claim 6,

I please change "a" to said as per A mend ment Role 116-. Signed andseale this 17th day of December 1974.

SEAL) fittest:

' McCOY M. GIBSONJR. I C. MARSHALL DANN attesting Officer Commissionerof Patents ORM PC7-1050 (10-69) USCOMM-DC 60376-P69 u 5 GOVERNMENTvnm'rma OFFICE: 930

5,789,002 Jan. 29,'197

Patent No. Dated Rudolf Weber et a1.

Inventor(s) It is certified that error appears in the above-identifiedpatent and that said Letters Patent are hereby corrected as shown below:

Feie ii l 7 Change "organic" to inorganic 3 2 Change "moi/liter" to.mMol/liter 3 62 Change ".(J) t v I I I 9 l Change ':'ejgected"j. to efi'ecvced i0 39 After "sulfonate's; please: insert sulfates, 1 i "In"should be If V V 23 +2 Delete the phrase '.'g1ycolurils having theformula" which was repeated in error. Q I 2M 16 8c In original I claim7, now known as claim 5, delete l7 the words "and hein from 5% to 95%hydrated".

This was cancelled as per Amendment Rule ll6. 22 In original claimlC),'now Known as claim 6,

i please change; "a" to said as per: amendment RLile 116. v Signed andsealedthis 17x1; day of December 1W4.

(SEAL) fittest:

' MCCOY M. GIBSONJR. c. MARSHALL DANN Attesting Officer Commissioner ofPatents ORM PO-OSO (10-69) USCOMM-DC 60376-5 69 u 5. GOVERNMENT rnmrmoOFFICE: 93 o

